1-methyl-phenylene-2,4-bis(triethoxysilyl propylene-3&#39;-ureylene)

ABSTRACT

THIS INVENTION RELATES TO NOVEL SILYL UREAS USEFUL AS FINISHING AGENTS. THESE COMPOUNDS ARE OF THE STRUCTURE:   R(-NH-CO-NH-Q)2   WHEREIN R IS A DIVALENT ORGANIC RADICAL SELECTED FROM THE GROUP CONSISTING OF: (A) CHAINS OF LINEAR POLYMERS TERMINATED ON BOTH ENDS BY ARYLENECARBAMOYL RADICALS OF THE STRUCTURE   -A-NH-CO-   WHEREIN A IS ARYLENE, AND (B) HYDROCARBON RADICALS, WHEREIN Q IS A SILYLALKYL RADICAL HAVING AFFIXED TO THE SILICON ATOM THREE SUBSTITUENTS SELECTED FROM THE GROUP CONSISTING OF ALKYL, ALKOXY, AND ARYLOXY AT LEAST ONE SUBSTITUENT OF WHICH IS SELECTED FROM THE GROUP CONSISTING OF ALKOXY AND ARYLOXY, WITH THE PROVISO THAT SAID ALKYL MOIETY OF THE SILYLALKYL CAN BE INTERRUPTED BY ETHER OXYGEN (-O-), AND IMINO GROUPS   -N(-R&#39;&#39;)-   WHEREIN R&#39;&#39; IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ARYL AND ALKYL.

United States Patent Cfice 3,576,033 l-METHYL-PHENYLENE-Z,4-BIS(TRIETHOXY- SILYL PROPYLENE-3'-UREYLENE) Giuliana C. Tesoro, Dobbs Ferry, N.Y., and Wing Kai Lee, Hackensack, N.J., assignors to J. P. Stevens & Co., Inc., New York, N.Y. N Drawing. Filed May 22, 1967, Ser. No. 640,388

Int. Cl. C0715 7/04; C08f 11/04; C08g 22/00 U.S. Cl. 260-448.8 1 Claim ABSTRACT OF THE DISCLOSURE This invention relates to novel silyl ureas useful as finishing agents. These compounds are of the structure:

R[-NH("3NHQ], wherein R is a divalent organic radical selected from the group consisting of:

(a) chains of linear polymers terminated on both ends by arylenecarbarnoyl radicals of the structure I -ANH-dl wherein A is arylene, and

(b) hydrocarbon radicals,

wherein Q is a silylalkyl radical having afiixed to the silicon atom three substituents selected from the group con- This invention relates to novel polyfunctional silanes useful as finishing agents and as interemdiates for preparing finishing agents.

More particularly this invention concerns novel silyl ureas of the structure:

wherein R is a divalent organic radical selected from the group consisting of:

(a) chains of linear polymers terminated on both ends by arylenecarbamoyl radicals of the structure ANH("3- wherein A is arylene, and (b) hydrocarbon radicals,

wherein Q is a silylalkyl radical having afiixed to the silicon atom three substituents selected from the group consisting of alkyl, alkoxy, and aryloxy, at least one substituent of which is selected from the group consisting of alkoxy and aryloxy, with the proviso that said alkyl chain can be interrupted by an ether oxygen (-0-), and imino groups wherein R' is selected from the group consisting of hydrogen, aryl and alkyl. These products, particularly those wherein at least two alkoxy groups are aifixed to the sill- 3,576,033 Patented Apr. 20, 1971 con atom, are useful as water repellents in cellulosics such as cotton and as dimensional stabilizers in proteinaceous substrates such as wool.

Within recent years a good deal of effort has been expended to develop water repellents for cellulosics and dimensional stabilizers for proteinaceous substrates. The development of reagents for these purposes extends the applications for which cotton and wool textile materials can be employed and for this reason is of considerable interest in the textile industry.

The development of water repellents for cellulosic garments particularly is difficult because of the rather unique combination of properties that is desired. Not only must the water repellent perform its primary purpose of resisting water, but in addition, the repellent should desirably:

(a) possess air permeability,

(b) upon application, have a smooth hand,

(c) show good durability after repeated launderings,

(d) be adaptable to existing application equipment, and

(e) lend itself to application by technically untrained personnel.

The novel products of this invention combine the desired traits and therefore represent an advance in the art.

It is an object of this invention, among others, to prepare novel products useful in improving the properties of both cellulosic and proteinaceous substances.

Another object of this invention is the preparation of homopolymers and copolymers of the above products which are useful as coatings and finishing agents.

A further object of this invention is the development of processes for improving the water resistance of fabrics and garments, particularly of those containing substantial proportions of cellulosic fibers, by the application of the above-mentioned silane-containing reagents.

Additional objects will become apparent to those skilled in the art after a perusal of this application.

In practice, a divalent organic diisocyanate reactant whose generic formula is:

and pressure conditions sufi'icient to produce the abovedefined silyl ureas of the structure:

wherein R and Q are as previously defined, is formed.

The diisocyanate reactants of the invention can be generically represented by the structure:

O=C=NR :0

wherein R is selected from two classes of radicals:

(a) chains of linear polymers terminated on both ends by arylenecarbamoyl radicals of the structure wherein A is arylene, and (b) hydrocarbon radicals.

The first group of values that the radical R can assume in the above formula comprises:

(a) Linear polymers terminated on both ends by arylenecarbamoyl radicals of the structure l ANH-iwherein the symbol A is arylene. This class can be more clearly expressed symbolically within the structure:

A-NH?!3O-Z(H]-NHA wherein A is arylene and Z in the above formula is selected from the group consisting of:

(1) polyalkyleneoxy or polyoxyalkylenes (C H O) wherein p ranges between 3 and 6, and n is between 2 and 200, (2) the chain of linear polyester wherein u is the degree of polymerization, averaging in range from about 6 to about 100.

The hydrocarbon radicals which comprise the second class (b) largely comprise two subclasses:

(1) Arylene radicals such as phenylene, methylphenylene, dimethylphenylene, and the like, and

(2) Aliphatic or cycloaliphatic radicals derived by polymerizing a saturated or unsaturated fat acid having 8 to 24 carbon atoms. The preparation of dimeric fat acids is disclosed in British Pat. 1,023,390, published Mar. 23, 1966. As indicated in the patent, the term fat acids" includes naturally occurring or synthetic saturates, ethylenically unsaturated and acetylenically unsaturated acids. The term polymeric fat radical is generic to the divalent, trivalent and polyvalent radicals of dimerized, trimerized and higher polymers of fat acids. Particularly of interest are members of the class of dimeric fat radicals, D, which are hydrocarbon radicals of dimerized fat acid. A preferred group of hydrocarbon radicals are of the stucture:

These structures are preferred because they readily lend themselves to the preparation of the corresponding diisocyanates.

The Q portion of the aminosilanes which are utilized as coreactants with the diisocyanates can also vary somewhat. For example, the following are illustrative of some permissible structures:

4 wherein R is selected from the group consisting of alkyl, aralkyl and aryl, and R, R and R which can be the same or difierent at any given time, are selected from the group consisting of aryl and alkyl groups, and C H is an alkylene radical in which p varies between 2 to 10 inclusive. Typical alkylene groups are:

and the like.

The preferred amino silanes are those within the structure:

wherein p is an integer less than 25.

The reaction conditions used to produce the novel silyl ureas of this invention are not critical and closely resemble those utilized in the addition of primary amines to diisocyanates in organic chemistry. Ordinarily, inert solvents such as the hydrocarbons and halogenated hydrocarbons are utilized, temperatures between about 20 C. and 75 C. are employed although higher and lower temperatures can be employed if desired. Moisture must be excluded from the reaction mixture. Near stoichometric proportions of reactants are used and ordinarily the reactions are run at atmospheric or near atmospheric pressure although the solvents are commonly stripped oil under reduced pressure. The reaction time varies according to the reactants employed and the temperature at which the reaction is run and therefore cannot be stated precisely. However, at temperatures of about 20-35" C. most reactions are complete within 4 to 24 hours. Longer times are not harmful.

While all of the silyl urea products are useful products, as in any large group, certain numbers of the group are to be preferred to the group as a whole. In this instance, products form the reaction of silanes of the formula:

wherein R is alkyl, aryl or alkoxyalkyl and C l-1 is a divalent alkylene radical containing from 3 to 25 carbon atoms, with a diisocyanate of the formula:

wherein D is a saturated or unsaturated hydrocarbon radical of dimeric fat acids, and w is a number selected from zero and one.

The resultant products are durable water repellents for cellulosics and can be prepared from inexpensive starting materials.

To better illustrate the Workings of this invention in more detail, the following preparation and application examples are submitted. In all instances, weight measurements are in parts by weight unless otherwise noted.

EXAMPLE 1 Preparation of the reactive polyfunctional silane produced by the addition of 3-(triethoxysilyl)propylamine to a diisocyanate derived from dimerized C unsaturated fatty acids The diisocyanate used as starting material is obtained from the C dibasic acid resulting from the controlled dimerization of C unsaturated fatty acids. The average value of y is approximately 66. A commercial grade having 14% -N:@0 is used containing less than 0.1% hydrolyzable chloride assaying at least 98%, and having a viscosity at 20 C. of 170 centipoises.

A solution consisting of 120 grams (0.2 mole) of the diisocyanate in 100 ml. of benzene is added dropwise at room temperature to a stirred solution of 88.4 grams (0.4 mole) of 3-(triethoxysilyl)propylamine in 100 ml. of benzene. After the addition is complete, the reaction mixture is stirred at room temperature for 8 hours. Then the solvent is partially removed by distillation under reduced First stage.The hydroxyl-terminated polybutadiene used as starting material is a technical grade having a hydroxyl content of 0.80 milliequivalent per gram, an iodine number of 395, and an average molecular weight of 32501250. The degree of polymerization, u, is 60:5 on

pressure. The residual material weighs 238 grams. It has h average a Solid Content of 168 grams, Corresponding t0 3 Yield Of The following procedure is used to convert the hydroxyl-terminated polybutadiene into essentially linear The absence of bands at 2270 in the infrared macromolecules terminated on both ends With isocyanate spectrum (Obtained \Vith chloroform as the solvent) ingroups A 2 1iter 3 neck flask equipped a stirrer a dicates that substantially all of the isocyanate groups thermometer a gas inlet tube and a dropping f l i react. Absorption bands at 3400 to 3100 crn. charactercharged with 00 grams f the hydroxypterminated polyistic of secondary amide groups are Observed- Those facts butadiene dissolved in 200 grams of dichloromethane. verify the di-substituted urea type of structure for the Toluene diisocyanate (43.6 grams, 0.25 mole of 2,4 and Product Showninthe above equaflon- 2,6 isomers in the ratio of 8/20) is added slowly while EXAMPLE 2 a stream of nitrogen is passed into the solution and the temperature is maintained at C. After completion of Preparation of the reactive polyfunctlonal silane produced the addition the Solution is stirred at to 0 Q for 8 by the addition of 3-(triethoxysilyl)propylamine to a h Ours dusocyanate denved from hnear polyester 20 Second stage-In order to replace the terminal isocyanate groups by reactive Si-containing groups, a solution II II consisting of (a) 159 grams of the intermediate produced 0 O l =c= in the first stage (namely the diisocyanate derived from Ismmmteterminated linear Wyester a polymer of 1,4-butadiene) and (b) 100 grams of di- 2H2NCH2CH2CH2 Si(0 C2115): [-0[omHimofi]vCmHimo-] (H1NH(:Hi

O I|\IHCNH (CH2) 3-81 (0 02115) a The isocyanate-terminated linear polyester used as startchloromethane is added dropwise at room temperature ing material has the type of structure indicated above: to a stirred solution of 26.5 grams (0.12 mole) of 3-(trimis about 6and ethoxysilyDpropylamine in 100 grams of dichloromet hv mainly 3 and 4. ane. After completion of the addition, the reaction mixture is allowed to stand overnight at room temperature. The ma'teflal h a 95% y, equivalent to Then solvent is distilled off under reduced pressure at mllllequlvalems of P gram. room temperature until the residual material attains con- A solution of 100 grams (0.226 equivalent) of that distant i h isocyanate in 100 grams of dichloromethane is added 40 Th absence f hands at 22 0 -l in the i f d dfopwlse at room temperature to a Stirred S01uti0n of spectrum (obtained with chloroform as the solvent) indigfams (0226 111016) of y )p y cates that substantially all of the isocyanate groups have Qmlne 111 100 grams of dlchloromethane- After p undergone reaction. Absorption bands at 3400 to 3100 tron of the addition, the reaction mixture is allowed to l Characteristic of secondary amide groups are i i- Stand Overnight at r00111 temperature- Then Solvent is dence, as would be expected from the presence of divalent fined Ofi under reduced Pressureureylene chains in the structure of this reactive bis(tri- The absence of bands at 2270 cm.- in the infrared ethoxysilyl) C0mp0und spectrum (obtained with chloroform as the solvent) indicates that substantially all of the isocyanate groups have EXAMPLE 4 reacted. Absorption bands at 3400 to 3100 Chaf- Preparation of the reactive polyfunctional silane produced acteristic of secondary amide groups, are observed, verifying the presence of ureylene chains by the addition of 3-(triethoxysilyl)propylamine to a 6 diisocyanate derived from a polymer of butadiene First stage:

by the addition of 3-(triethoxysilyl)propylamine to toluene diisocyanate Second stage:

A solution of 87 grams (0.5 mole of 2,4 and 2,6 isomers in the ratio of 80/20) of toluene diisocyanate in 100 grams of dichloromethane is added slowly to 221 grams (1.0 mole) of 3-(triethoxysilyl)propylamine in 600 grams of dichloromethane at room temperature. Analysis, in the manner used in Example 3, confirms that the product had the structure shown above. This reactive polyfunctional silane, namely 1,1-(methyl-m-phenylene)bis- [3-[3-(triethoxysilyl)propyl]urea], is applied to cotton, imparting water repellency, and to wool, minimizing shrinkage in laundering.

The finishing agents of this invention can be applied to the textile substrate by a number of conventional application methods well known in the textile art. These include, but are not limited to brushing, spraying, padding, coating and the like. The agents can be in the form of solutions, slurries, suspensions, emulsions, or the like, Where appropriate; the main requirement being that an effective quantity of finishing agent is deposited on the textile substrate treated. By an effective quantity is meant, that quantity of reagent required to impart the desired characteristics to the treated substrate. Because of the experimental variables and the effect sought, this amount cannot be stated with precision. However, in the case of cotton, depending upon the reagent, an effective water repelling quantity ranges between /2 to by weight of reagent based upon the weight of the treated substrate. Usually, the amount employed ranges between 26%, by weight of reagent, although the upper limit of reagent concentration is primarily limited by economic considerations. Similarly, an effective quantity of dimensional stabilizing reagent that is required to stabilize proteinaceous substrates ranges between /2 to 10% by weight of reagent based upon the treated substrate, but usually between 2-6% by weight of reagent. Again, the upper limit of reagent being governed by economic limitations. Ordinarily, it is convenient to utilize an inert solvent where solutions are employed. The choice of solvent is not critical as long as it possesses good solubilizing char acteristics and it is devoid of reactive groups which could react with the silyl groups. Illustrative inert solvents include tertiary amides such as N,N-dimethylformarnide, N,N-dimethylacetamide, 1 methyl-2-pyrrolidinone, 1,5- dimethyl-Z-pyrrolidinone, cyclic ethers such as the dioxanes and trioxanes, aliphatic ethers such as cn ocn cn ocur and sulfoxides such as dimethyl sulfoxide.

A convenient mode of application is padding. In this procedure, the textile is impregnated with a solution of the reagent in inert solvent, the rolls of the padder being set to the desired wet pickup. The treated textile is dried, usually between about 40 C. to 85 C. and cured above 100 C. The cured, dried samples are usually moisture conditioned to the desired moisture content by exposing them to an appropriate humidity level.

In addition to the finishing reagents of this invention, the padding bath can contain one or more various optional textile adjuvants such as softeners, conditioners, surfactants and the like. Since these reagents are not critical to the success of this invention, no attempt is made to enumerate the various adjuvants that can be employed. It will suffice to say, exhaustive lists of these can be found in the technical and patent literature.

EVALUATION TEST METHODS Dry cleaning Durability test: Commercial equipment and formulation are used.

Flex abrasion resistance in cycles ASTM D-117561T; 0.5-pound head Weight and 2- pound toggle tension on Stoll Flex abrader.

8 Laundering method for cotton having water repellent finish Home-type machine: low (ll-gallon) water level; 4- pound load; Fab or Tide detergent; normal agitation; 12-minute wash cycle at 60 rinse at 43:3 C.; normal rinse and spin cycle; tumble-dry at 74 C.; fiat-bed pressing at 135 to 149 C. for 5 seconds without steam; recondition for at least 4 hours (relative humidity at 65i2%, 21:1 C.).

Laundering method for washable woolens First, the swatch is conditioned for at least 4 hours (relative humidity at 65:2%, 21:1" C.), and markings are applied 10 inches apart, then: laundered in hometype machine; full water level; 5-pound load; Fab or Tide detergent; 15-minute wash at 40 C.; running suds 1.5 to 2 inches; automatic rinse; dried fiat on horizontal screen; fiat-bed pressing at 135 to 149 C. for 5 seconds without steam; reconditioned for at least 4 hours and remeasured.

The number of cycles (as 0, 1 or 10), of laundering and tumble drying is indicated by no L, IL, or 10L, respectively.

Shrinkage in laundering in percent See Laundering Method for Washable Woolens above.

Stiffness test Results in milligrams per centimeter: ASTM D1388- 55T cantilever method.

Water repellency spray rating AATCC test method 22-1964, Manual of the American Association of Textile Chemists and Colorists, 1964 edition, pages B-130-131.

Xylene extraction Refiuxing for 2 hours.

Parts and percentages By weight, unless otherwise noted.

Abbreviations in tables When used individually, F means filling direction, and W means warp direction. Note the special meanings of the following 3-letter abbreviations.

OWB: On the weight of the bath. The term is applied when expressing the concentration (percent) of an ingredient in the liquid mixture used for impregnating samples of fabric.

OWF: On the weight of fiber (or fabric), i.e., based on the weight of fabric prior to padding. The percentage of a reagent OWF means the add-on of solids expressed in percent on the dry basis.

WPU: Wet pickup, i.e., the wet add-on (usually expressed in percentage OWF) which is the gain from solution penetrating the fabric, measured immediately after padding. As used herein, padding consists of the dual process of impregnating the fabric by passing it through a pad bath and then passing the wet fabric through squeeze rollers or wringers.

When expressed in percent, the foregoing terms are related as follows:

(Percent OWB) multiplied by (percent WPU)/ =(percent OWF).

EXAMPLE 5 Application of the disilane of Example 1 to cotton to impart water repellency Samples of 100% cotton fabric (8 ounces per square yard in a twill weave) are conditioned with the relative humidity at 65 12% (2111 C.) and weighed on an analytical balance. Then they are impregnated with a 5% (active basis, by weight) solution in p-dioxane of the disilane of Example 1. The impregnation is effected on a EXAMPLE 6 laboratory padder. Its rolls are set at a pressure which results in a wet pickup of 62 to 67%, as detailed in the accompanying table. The fabric samples so treated are dried at 50 to 60 c. Samples of the B, c, and D series Samples of 100% cotton fabric (8'ounces p square are overpadded with aqueous dispersions (pH between 6 y in a twin Weave) are Processed Similarly to the P and 7) of catalysts, as noted in the following table. (When Cedllfe 0f EXaIhple 5, except that the disilane 0f the pH of the aqueous dispersion of the catalyst have to ample 2 is used instead of that Of Example Application of the disilane of Example 2 to cotton to impart water repellency be lowered to 6.5 $0.5, this is accomplished by means of dlmethyl-formamide IS the solvent instead of p-dl Xa acetic acid.) and (c) certain percentages are different, as is apparent Catalysts I Xylene extraction Disilane of Ex. 1 Organo- Metal Heat Actual Loss of Water repellency spray rating functional org. salt treatment weight Weight weight WPU, OWF, type 81, type 128, (temp. of gain, loss, gain, Originally After After dry percent percent percent percent curing), 0. percent percent percent (no L) laundering cleaning 67 3. 35 None None 150 3. 97 0/50 0/50 70 62 3. None None 177 4 53 0. 70 16 0/50 0/50 70 63 3. None None Steamed 3. 57 50 50 70 62 3. 10 0. 1 None 150 4 06 70 70 70 63 3. 15 0. 1 None 177 3. 50 0. 56 17 70 50 70 62 3 10 0.1 None Steamed 3 38 50/70 50 7O 62 3 10 None 0.6 150 3 34 50 50 50/70 63 3 15 None 0.6 177 4 18 0 52 13 50 50 50 6-1 3 20 None 0.6 Steamed 3.30 /70 50 50/70 63 3 15 0. 1 0. 6 150 3 29 50 50/70 63 3 15 0.1 0. 6 177 3.10 0.21 7 7 70 50/70 62 3 10 0.1 0.6 Steamed 3. 52 70 50/70 50/70 0 1 Catalysts: Products of Dow Corning Corp. (50% solids andpyridine carrier for type 81: 28% solids for type 128).

All samples are dried at 50 to C., then cured on a from the tabulated data. Samples are either cured for 5 frame for 5 minutes at the temperature shown in the table, minutes at approximately 163 C. or steamed for 10 minor the samples are exposed to dry steam for 15 minutes. utes, as indicated under heat treatment.

Disilane of Example 2 Catalysts 2 Water repellency spray rating Organo- Metal org. functional salt type OWB, WPU, OWF, type 81, 128, Heat treat- Originally After Sample percent percent percent percent percent ment 2 (no L) laundering Cured 50 50 A 5.5 No None {steameduu 50 50 B 5. 5 5s 3. 2 0. 1 None lg fi o 5. 5 5s 3. 2 None 0. 6 {gig D 5.5 0.1 o.o{

E 1. 7 e0 1. 0 None None 28 8 F 1.7 0.1 None g G 1. 7 e0 1. 0 None 0. 6 3 38 Cured 7 H 7 {Steamed 70 0/50 Control Unheated..- 0 0 l Concerning catalysts, see footnote to table of Example 5.

2 Cured 5 minutes at 163 C., or steamed 10 minutes.

3 Major portions of test area of cured Sample G (no L) were wetted through at certain spray points.

Next, they are rinsed thoroughly in p-dioxane and then in EXAMPLE 7 water. After the samples have been allowed to dry, they are Application of the disilane of Example 2 to Wool to conditioned with the relative humidity at 65%. The con- Prevent Shrinkage to laundering ditioned samples are weighed on an analytical balance to determine weight gains. Treatment data are shown in the first section of the table. Performance with respect to Sample of wool fabric (6.15 ounces per square yard in a plain weave) are treated similarly to the cotton samples of Example 6, except as is evident from the de- Water repellency is ShOWn in the 00nd Section 0f t tails of the following table, which includes evaluation table. results.

Catalysts 1 Shrinkage in Disilane of Example 2 laundering,

Organo- Metal org. Actual percent functional salt type weight OWB, WPU, OWF, type 81, 128, Heat treatgain, Sample percent percent percent percent percent ment percent W F A 2. 3 109 3.1 None 2 8 B 2.3 0.1 C 2.8 None D 2. s 110 3.1 0.1 5 83;: E 0. 9 112 1. 0 None 3- g g 1 Concerning catalysts, see footnote to table of Example 5. Cured 5 minutes at 163 C., or steamed 10 minutes.

Catalysts 1 Disllane of Example 2 Organo- Metal Actual Shrinkage ln functional org. salt weight laundering, percent OWB, WPU, OWF, type 81, type 128, Heat gain, Sample percent percent percent percent percent treatment 2 percent W F G 0.9 112 1. None 8.0 2. H 0.9 112 1. 0 0. 1 O 1. 5 r 5. 5 a 5. 8 None 8- 8 g; 8 6. 11 5. 5 0. 5 J d 5.27 56.5

ure 5. 6 .5 K 5 6 {%tean$ed 5. 1o 7. 5 5 ure 6. 83 5.5 .5 102 istearncdnfl 5.43 so 1.5 Untreated control 3 11. 0 7. 0

1 Concerning catalysts, see footnote to table of Example 5. 2 Cured 5 minutes at 163 0., or steamed 10 minutes. 3 100% wool fabric; plain weave.

EXAMPLE 8 Application of the disilane of Example 4 to cotton to impart water repelleney Three samples of 100% cotton 8-ounce twill are used. One was processed in a manner similar to that set forth C atalysts Shrinkage in laundering, percent Disilane of Example 4 Organo- Metal functional org. salt 1 wash 10 washes Wool fabric OWB, WPU, OWF, type 81, type 128, sample percent percent percent percent percent W F W F 2. 7 112 3. 0 None None 2. 5 0. 5 4. 5 1. 5 2. 7 111 3. 0 0. 1 None 1. 5 +0. 5 6. 0 0. 5 2. 7 111 3. 0 None 0. 6 2. 0 0. 5 5. 5 1. 5 D 2. 7 110 3. 0 0. 1 0.6 2. 5 +0. 5 5. 0 0. 5 Control untreated 13. 5 9. 0 30. 5 28. 5

l Concerning catalysts, see footnote to the table of Example 5. Acetic acid was used to adjust the pH oi the catalyst dispersion to 5510.5.

in Example 5, except that (a) the disilane of Example 4 was utilized instead of the disilane of Example 1, (b) N,N-dimethyl-formamide is the solvent rather than pdioxane, and (c) "the percentages are as follows: The concentration is 5.45% OWB, the WPU is 56%, giving 3.05% OWF. The sample is dried at 50 to 60 C. Next, the sample is overpadded with an aqueous dispersion consisting of 0.7% of each of the catalysts described in the table to Example 5. (The pH of the dispersion of the catalysts is adjusted to 5.51:0.5 by the addition of acetic acid prior to overpadding.) The overpadded sample is dried at 50 to 60 C., then is cured on a frame for 5 minutes at approximately 164 C. The remaining processing details followed the procedure of Example 5. The spray rating of this treated sample in the test for water repellency is 50. In contrast, the second sample (untreated 100% cotton 8-ounce twill) has a spray rating of zero.

The third sample is treated similarly to the first sample, except that the concentration in the pad bath is 5.0% OWB, WPU is 58% giving 2.9% OWF, and the percentages of Catalyst 81 and Catalyst 128 are only 0.1 and 0.6%, respectively, in the aqueous dispersion used for overpadding. After subsequent processing as described for the first sample, this third sample has a spray rating of 70 after one laundering and also after 5 launderings as well.

EXAMPLE 9 Application of the disilane of Example 4 to wool to minimize shrinkage in laundering Samples of 100% wool fabric (6.15 ounces per square yard in a plain weave) are conditioned with the relative humidity at 65:2% (21:1" C.) and weighed. They are padded with a solution consisting of the disilane of Example 4 (2.7 parts by weight), toluene (8.1 parts by weight) and N,N-dimethyl-formamide (DMF, 89.2 parts As the above examples and previous discussion indicate, the inventive compositions are advantageous in several respects. For example, the products can be prepared from available starting materials and are formed under relatively flexible reaction conditions. In addition, the products lend themselves to textile modification since they undergo their reactions including polymerization under relatively mild conditions, enabling them to be applied by non-technically trained personnel. Finally, the silane products afi'ord durable Water repellency to textile substrate in economically feasible concentrations.

The metes and bounds of this invention, in both its product and process aspects, are best determined by refference to the claim which follows.

What is claimed is:

(CzH5O-);SiCH CH CH NH-fi-NH]; Q

References Cited UNITED STATES PATENTS 3,208,971 9/1965 Gilkey 61; a1. 260448.2X 3,243,429 3/1966 Ham 260448.2X 3,278,484- 10/1966 Tesoro 26046.5 3,413,265 11/1968 BertOZZi 26046.5 3,440,261 4/ 1969 Saam 260-448.2

TOBIAS E. LEVOW, Primary Examiner W. F. W. BELLAMY, Assistant Examiner US. Cl. X.R.

26046.5E, 77.5, 448.2N; ll714l; 161-206, 209 

